Post-planarization densification

ABSTRACT

Processes for forming high density gap-filling silicon oxide on a patterned substrate are described. The processes increase the density of gap-filling silicon oxide particularly in narrow trenches. The density may also be increased in wide trenches and recessed open areas. The densities of the gap-filling silicon oxide in the narrow and wide trenches/open areas become more similar following the treatment which allows the etch rates to match more closely. This effect may also be described as a reduction in the pattern loading effect. The process involves forming then planarizing silicon oxide. Planarization exposes a new dielectric interface disposed closer to the narrow trenches. The newly exposed interface facilitates a densification treatment by annealing and/or exposing the planarized surface to a plasma.

CROSS REFERENCE TO RELATED APPLICATION

This application is a nonprovisional of, and claims the benefit of thefiling date of U.S. Provisional Patent Application No. 61/248,693, filedOct. 5, 2009, entitled “POST-PLANARIZATION ANNEAL” by Jingmei Liang etal., the entire disclosure of which is incorporated herein by referencefor all purposes.

BACKGROUND OF THE INVENTION

Semiconductor device geometries have dramatically decreased in sizesince their introduction several decades ago. Modern semiconductorfabrication equipment routinely produce devices with 45 nm, 32 nm and 28nm feature sizes; new equipment is being developed and implemented tomake devices with even smaller geometries. The decreasing feature sizesresult in structural features on the device having decreased spatialdimensions. The widths of gaps and trenches on the device narrow to apoint where the aspect ratio of gap depth to its width becomes highenough to make it challenging to fill the gap with dielectric material.The depositing dielectric material is prone to clog at the top beforethe gap completely fills, producing a void or seam in the middle of thegap.

Over the years, many techniques have been developed to avoid havingdielectric material clog the top of a gap, or to “heal” the void or seamthat has been formed. One class of approaches typically involvesseparate depositions surrounding etch back processes. This results in adep-etch-dep sequence which may impose tighter process specificationsfor both deposition and etch. Another approach has been to start withhighly flowable precursor materials that may be applied in a liquidphase to a spinning substrate surface (e.g., SOG deposition techniques).These flowable precursors can flow into and fill very small substrategaps without forming voids or weak seams. However, once these highlyflowable materials are deposited, they may need to be cured and hardenedinto a solid dielectric material.

There is a need to produce alternative gap-filling films having lessstress by modifying the deposition process and/or subsequent processing.There is also a need for these process sequences to produce films havingsimilar properties in narrow and wide trenches. This and other needs areaddressed in the present application.

BRIEF SUMMARY OF THE INVENTION

Processes for forming high density gap-filling silicon oxide on apatterned substrate are described. The processes increase the density ofgap-filling silicon oxide particularly in narrow trenches. The densitymay also be increased in wide trenches and recessed open areas. Thedensities of the gap-filling silicon oxide in the narrow and widetrenches/open areas become more similar following the treatment whichallows the etch rates to match more closely. This effect may also bedescribed as a reduction in the pattern loading effect. The processinvolves forming then planarizing silicon oxide. Planarization exposes anew dielectric interface disposed closer to the narrow trenches. Thenewly exposed interface facilitates a densification treatment byannealing and/or exposing the planarized surface to a plasma.

Embodiments of the invention include methods of processing asilicon-and-oxygen-containing layer on a patterned substrate having anarrow trench and a recessed open area. The methods include forming asilicon-and-oxygen-containing layer on the patterned substrate includingin the narrow trench and in the recessed open area. The methods includeplanarizing the silicon-and-oxygen-containing layer leaving a narrowgapfill portion in the narrow trench and a wide gapfill portion in therecessed open area. Planarizing the silicon-and-oxygen-containing layerincludes removing a portion of the silicon-and-oxygen-containing layerabove the narrow trench and exposing a post-planarization dielectricinterface disposed closer to the narrow trench then a correspondingpre-planarization dielectric interface. The methods further includetreating the substrate, after the planarizing operation, to increase adensity of the narrow gapfill portion. During the treatment, thepost-planarization dielectric interface disposed closer to the narrowtrench allows the narrow gapfill portion to become denser than had thesubstrate been treated before the planarizing operation.

Additional embodiments and features are set forth in part in thedescription that follows, and in part will become apparent to thoseskilled in the art upon examination of the specification or may belearned by the practice of the disclosed embodiments. The features andadvantages of the disclosed embodiments may be realized and attained bymeans of the instrumentalities, combinations, and methods described inthe specification.

BRIEF DESCRIPTION OF THE DRAWINGS

A further understanding of the nature and advantages of the presentinvention may be realized by reference to the remaining portions of thespecification and the drawings wherein like reference numerals are usedthroughout the several drawings to refer to similar components. In someinstances, a sublabel is associated with a reference numeral and followsa hyphen to denote one of multiple similar components. When reference ismade to a reference numeral without specification to an existingsublabel, it is intended to refer to all such multiple similarcomponents.

FIG. 1 is a flowchart illustrating selected steps for processing asilicon-containing film according to disclosed embodiments.

FIG. 2 is a cross-sectional schematic of an etched silicon oxide filmand an etched silicon oxide film prepared according to disclosedembodiments.

FIG. 3 is another flowchart illustrating selected steps for processing asilicon oxide gapfill film according to disclosed embodiments.

FIG. 4 shows a substrate processing system according to disclosedembodiments.

FIG. 5A shows a substrate processing chamber according to disclosedembodiments.

FIG. 5B shows a showerhead of a substrate processing chamber accordingto disclosed embodiments.

DETAILED DESCRIPTION OF THE INVENTION

Processes for forming high density gap-filling silicon oxide on apatterned substrate are described. The processes increase the density ofgap-filling silicon oxide particularly in narrow trenches. The densitymay also be increased in wide trenches and recessed open areas. Thedensities of the gap-filling silicon oxide in the narrow and widetrenches/open areas become more similar following the treatment whichallows the etch rates to match more closely. This effect may also bedescribed as a reduction in the pattern loading effect. The processinvolves forming then planarizing silicon oxide. Planarization exposes anew dielectric interface disposed closer to the narrow trenches. Thenewly exposed interface facilitates a densification treatment byannealing and/or exposing the planarized surface to a plasma.

Dielectric within a trench may possess different properties fromdielectric within an open area (or a wide trench). This may result fromthe more restricted geometry within a narrow trench compared to a widetrench. Following a planarizing step (e.g. a planarizing etch orchemical-mechanical polishing—CMP), the additional exposure to thesurrounding atmosphere provides the ability to process the film stack soas to increase the density of the gapfill material and to make theproperties of the material within the narrow trench and within the widetrench (or recessed open area) more similar. Dielectric films whichbenefit from the thermal processing include relatively less dense filmssuch as silicon oxide deposited with PECVD, APCVD, FCVD, SOG etc. Themethods may provide particular utility to films which are flowableduring deposition such as flowable CVD (FCVD) and spin-on glass (SOG).The difference between properties within and outside the narrow trenchmay be evaluated by comparing the wet etch rate in a wet etchcomprising, e.g., hydrogen fluoride HF. Silicon oxide will be used as ashorthand throughout to mean a silicon-and-oxygen-containing layer andincludes films such as silicon oxycarbide and silicon oxynitride.

Without binding the coverage of the claims to hypothetical processmechanisms, heating a film stack following planarization is thought torestructure the network within the dielectric resulting in a reductionin wet buffered oxide etch (BOE) rate especially within trenchesAnnealing dielectric films at high temperatures has been found totransition a film from tensile to compressive stress. The removal ofmaterial like hydrogen from the dielectric is another possible mechanismand may occur at the same time as the restructuring. The region withinnarrow trenches is found to benefit more than the region within widetrenches and open areas. Silicon oxide is an example of a dielectricwhich benefits from a post-CMP anneal. The density of silicon oxidewithin restricted geometries (like narrow trenches) is increased duringthe post-CMP anneal which may cause the reduction in wet etch rate(WER). The physical curvature of the substrate as a whole may also bemitigated by the presence of the compressive layers during formation ofthe film and during subsequent processing.

Exposing the planarized dielectric surface to a plasma has also beenfound to provide similar benefits with regard to the densification ofthe gapfill dielectric. Ion bombardment of the planarized surface in theplasma-excited atmosphere appears to increase the density of the gapfilldielectric. Adding oxygen to the atmosphere excited by the plasma helpsfurther increase the density in some cases by supplying oxygen which isincorporated into the silicon oxide. The oxygen can be incorporated intovoids present in a relatively porous gapfill dielectric and/or maydisplace less-dense constituents which may also be more weakly bound tothe material in the gapfill dielectric. Adding hydrogen in combinationwith the oxygen may also help increase the density of the gapfilldielectric as a result of the increase in moisture content.

Additional details will be provided in the course of describing severalexemplary methods. FIG. 1 is a flowchart showing selected steps in amethod 100 of making silicon oxide films according to embodiments of theinvention. The method 100 includes transferring a patterned substratehaving narrow gaps or trenches and recessed open areas into a reactionchamber 102. The recessed open areas may be wide trenches having a widthgreater than 50 nm, 100 nm, 200 nm, 500 nm or 1000 nm, in differentembodiments. The narrow trench may have a width less than 100 nm, 70 nm,50 nm, 35 nm, 25 nm or 20 nm, in different embodiments. The narrowtrench may have a height and width that define an aspect ratio (AR) ofthe height to the width (i.e., H/W) that is significantly greater than1:1 (e.g., 5:1 or more, 6:1 or more, 7:1 or more, 8:1 or more, 9:1 ormore, 10:1 or more, 11:1 or more, 12:1 or more, etc.). Filling thenarrow trenches and recessed open areas begins by concurrently providinga carbon-free silicon precursor and a radical nitrogen precursor tosubstrate processing region 104.

The carbon-free silicon precursor may be, for example, asilicon-and-nitrogen precursor, a silicon-and-hydrogen precursor, or asilicon-nitrogen-and-hydrogen containing precursor, among other classesof silicon precursors. Specific examples of these precursors may includesilyl-amines such as H₂N(SiH₃), HN(SiH₃)₂, and N(SiH₃)₃, among othersilyl-amines. These silyl-amines may be mixed with additional gases thatmay act as carrier gases, reactive gases, or both. Examples ofadditional gases may include H₂, N₂, NH₃, N₂H₄, He, and Ar, among othergases. Examples of carbon-free silicon precursors may also includesilane (SiH₄) either alone or mixed with other silicon-containing gases(e.g., N(SiH₃)₃), hydrogen-containing gases (e.g., H₂), and/ornitrogen-containing gases (e.g., N₂, NH₃, N₂H₄). Carbon-free siliconprecursors may also include disilane, trisilane, higher-order silanes,and chlorinated silanes, alone or in combination with one another or thepreviously mentioned carbon-free silicon precursors. Thesilicon-precursor may be oxygen-free in addition to carbon-free. Thelack of oxygen results in a lower concentration of silanol (Si—OH)groups in the silicon-and-nitrogen layer formed from the precursors.Excess silanol moieties in the deposited film can cause increasedporosity and shrinkage during post deposition steps that remove thehydroxyl (—OH) moieties from the deposited layer.

The radical-nitrogen precursor is a nitrogen-radical containing speciesthat was generated outside the reaction chamber from a more stablenitrogen precursor. For example, a stable nitrogen precursor such a NH₃may be activated in a plasma unit outside the reaction chamber to formthe radical-nitrogen precursor, which is then transported into thereaction chamber. The stable nitrogen precursor may also be a mixturecomprising NH₃ & N₂, NH₃ & H₂, NH₃ & N₂ & H₂ and N₂ & H₂, in differentembodiments. Hydrazine (N₂H₄) may be used in lieu of or in addition toNH₃, and may be combined with N₂ and/or H₂ as listed above. Theradical-nitrogen precursor produced comprises plasma effluents whichinclude one or more of .N, .NH, .NH₂, etc., and may also be accompaniedby ionized species formed in the plasma.

A radical precursor may be a radical-nitrogen precursor if it includesnitrogen supplied with the aforementioned precursors to the remoteplasma region. Generally speaking, a radical precursor which does notinclude nitrogen will also allow a silicon-and-nitrogen-containing layerto be formed. The radical precursor is generated in a section of thereaction chamber partitioned from a deposition region where theprecursors mix and react to deposit the silicon-and-nitrogen layer on adeposition substrate (e.g., a semiconductor wafer). In an embodimentwhere the radical precursor is a radical-nitrogen precursor, a stablenitrogen precursor is flowed into the remote plasma region and excitedby a plasma. The stable nitrogen precursor (and the radical-nitrogenprecursor) may also be accompanied by a carrier gas such as hydrogen(H₂), nitrogen (N₂), argon, helium, etc. A radical-nitrogen precursorformed from an input gas consisting essentially of nitrogen (N₂) (withor without additional inert carrier gases) has also been found toproduce beneficial films in disclosed embodiments. The radical-nitrogenprecursor may also be replaced by a radical precursor formed from aninput gas consisting essentially of hydrogen (H₂) (and optionally inertcarrier gases) in embodiments where the silicon-containing precursorprovides the nitrogen needed in the desired film. The precursors flowinginto the plasma to be excited may be referred to herein as plasmaprecursors and the radical precursors flowing out of the plasma may bereferred to as plasma effluents.

In the reaction chamber, the carbon-free silicon precursor and theradical-nitrogen precursor mix and react to deposit asilicon-and-nitrogen containing film on the deposition substrate 106.The deposited silicon-and-nitrogen-containing film may depositconformally with some recipe combinations in embodiments. In otherembodiments, the deposited silicon-and-nitrogen containing film hasflowable characteristics unlike conventional silicon nitride (Si₃N₄)film deposition techniques. The flowable nature of the formation allowsthe film to flow into narrow gaps, trenches and other structures on thedeposition surface of the substrate. The flowable film fills gaps withhigh aspect ratios without creating voids or weak seams around thecenter of the filling material, in embodiments. The flowable film isless likely to prematurely clog the top of a narrow gap or trench.

The flowability may be due to a variety of properties which result frommixing a radical-nitrogen precursors with carbon-free silicon precursor.These properties may include a significant hydrogen component in thedeposited film and/or the presence of short chained polysilazanepolymers. These short chains grow and network to form more densedielectric material during and after the formation of the film. Forexample the deposited film may have a silazane-type, Si—NH—Si backbone(i.e., a Si—N—H film). When both the silicon precursor and theradical-nitrogen precursor are carbon-free, the depositedsilicon-and-nitrogen containing film is also substantially carbon-free.Of course, “carbon-free” does not necessarily mean the film lacks eventrace amounts of carbon. Carbon contaminants may be present in theprecursor materials that find their way into the depositedsilicon-and-nitrogen precursor. The amount of these carbon impuritieshowever are much less than would be found in a silicon precursor havinga carbon moiety (e.g., TEOS, TMDSO, etc.).

Following the deposition of the silicon-and-nitrogen-containing layer,the deposition substrate may undergo a treatment in an oxygen-containingatmosphere 108. The substrate is initially cured in an ozone-containingatmosphere in disclosed embodiments. The deposition substrate may remainin the substrate processing region for curing, or the substrate may betransferred to a different chamber where the ozone-containing atmosphereis introduced. The curing temperature of the substrate may be less thanor about 400° C., less than or about 300° C., less than or about 250°C., less than or about 200° C. or less than or about 150° C. indifferent embodiments. The temperature of the substrate may be greaterthan or about room temperature, greater than or about 50° C., greaterthan or about 100° C., greater than or about 150° C. or greater than orabout 200° C. in different embodiments. Any of the upper bounds may becombined with any of the lower bounds to form additional ranges for thesubstrate temperature according to additional disclosed embodiments. Noplasma or substantially no plasma is applied to the substrate processingregion during curing, in embodiments, to avoid generating atomic oxygenwhich may close the near surface network and thwart subsurfaceoxidation. The flow rate of the ozone into the substrate processingregion during the cure step may be greater than or about 200 sccm,greater than or about 300 sccm or greater than or about 500 sccm whichis typically accompanied by a larger flow of relatively more stablemolecular oxygen. The partial pressure of ozone during the cure step maybe greater than or about 10 Torr, greater than or about 20 Torr orgreater than or about 40 Torr. Under some conditions (e.g. betweensubstrate temperatures from about 100° C. to about 200° C.) theconversion has been found to be substantially complete so a relativelyhigh temperature anneal in an oxygen-containing environment may beunnecessary in embodiments. In some embodiments, the planarization mayoccur following the ozone treatment just described.

In other embodiments, the exposure to an oxygen-containing atmospherecontinues in the form of a higher temperature treatment. Followingcuring of the silicon-and-nitrogen containing layer, the depositionsubstrate may be annealed in an oxygen-containing atmosphere 110. Thedeposition substrate may remain in the same substrate processing regionused for curing when the oxygen-containing atmosphere is introduced, orthe substrate may be transferred to a different chamber where theoxygen-containing atmosphere is introduced. The oxygen-containingatmosphere may include one or more oxygen-containing gases such asmolecular oxygen (O₂), ozone (O₃), water vapor (H₂O), hydrogen peroxide(H₂O₂) and nitrogen-oxides (NO, NO₂, etc.), among otheroxygen-containing gases. The oxygen-containing atmosphere may alsoinclude radical oxygen and hydroxyl species such as atomic oxygen (O),hydroxides (OH), etc., that may be generated remotely and transportedinto the substrate chamber. Ions of oxygen-containing species may alsobe present. The oxygen anneal temperature of the substrate may be lessthan or about 1100° C., less than or about 1000° C., less than or about900° C. or less than or about 800° C. in different embodiments. Thetemperature of the substrate during the oxygen anneal may be greaterthan or about 500° C., greater than or about 600° C., greater than orabout 700° C. or greater than or about 800° C. in different embodiments.Any of the upper bounds may be combined with any of the lower bounds toform additional ranges for the substrate temperature according toadditional disclosed embodiments. The patterned substrate mayadditionally be annealed in an inert environment at even highertemperatures. The temperature of the substrate during the inert annealmay be greater than or about 800° C., greater than or about 900° C.,greater than or about 1000° C. or greater than or about 1100° C. indifferent embodiments.

The patterned substrate is then transferred to a chemical-mechanicalpolishing (CMP) tool. The silicon oxide on the patterned substrate ispolished to planarize the silicon oxide layer 110. Planarizing processessuch as CMP typically remove material which extends farther away fromthe substrate more rapidly than recessed material which can result ingreater planarity over a selectable lateral length scale. The laterallength scale is typically significantly less than the “length” ordiameter of the substrate. Other techniques may be used to planarize thesurface including etch processes tuned to preferentially remove siliconoxide which extends above recessed areas. Material from both extendedand recessed areas is removed in embodiments. After planarization usingCMP, a post-planarization dielectric interface is formed disposed closerto the patterned substrate than the pre-polish interface.

The post-planarization dielectric interface allows the material within(especially) narrow trenches to be treated to increase density beyondwhat would be possible prior to the planarization. The substrate may becured and annealed 112 as described before planarization including allthe process parameter ranges and atmospheres presented the discussionassociated with operation 108. The post-planarization dielectricinterface enables the same embodiments presented above to furtherincrease the density of material in all recessed areas but especiallywithin the narrow trenches. The presence of the oxygen combined with thecloser proximity of the post-planarization dielectric interface to thenarrow trenches, may allow unreacted nitrogen left in the film to befurther displaced by oxygen. In other words, the oxygen exposure mayfurther the conversion from silicon-and-nitrogen-containing layer tosilicon-and-oxygen-containing layer in regions which were simply too faraway from the interface before planarization. The additionaldensification made possible after CMP shows that the SiO₂ network withina trench may be maintained by the overlying dielectric layer. Once theoverlying layer has been removed, the SiO₂ within the trench is free torestructure during the post-CMP anneal. The restricted geometry of thetrench may help to constrain network restructuring during the pre-CMPanneal while the renewed exposure after CMP allows significantadditional network restructuring to occur. The oxygen-containingatmosphere may include the oxygen-containing compounds and radicalsdescribed earlier. The oxygen-containing atmosphere may further includehydrogen, in embodiments, to increase moisture, facilitate networkrestructuring and increase the density within recessed areas.

The anneal before the planarization step may be modified as a result ofthe introduction of the post-planarization anneal. Rather thandensifying the film in preparation for downstream processing, thepre-CMP anneal only needs to densify the film so it will tolerate theCMP step. This may reduce or eliminate the need for the high temperatureportion of the treatment. In embodiments, the film requires a lowtemperature cure in an ozone-containing environment. In otherembodiments, the film requires a low temperature cure in anozone-containing environment and a low temperature anneal in anoxygen-containing environment. In addition to delamination and polishinguniformity considerations, the pre-CMP anneal should be chosen to allowtolerable defect levels. Inclusion of a post-planarization anneal canpotentially be used to reduce, mitigate, control or prevent filmcracking for flowable films during processing since the pre-CMP annealmay have a lower thermal load than the post-CMP anneal. The post-CMPanneal may possess a high temperature, but the thickness of the film isreduced which may reduce the chance of film cracking during the anneal.

In some embodiments, the patterned substrate comprises a narrow trenchand a recessed open area, each of which is filled with silicon oxide asdescribed above. As a result of a variety of effects, the density of thesilicon oxide within the narrow trench may be less than the density ofthe silicon oxide within the recessed open area. This can be determinedby measuring the wet etch rate when each material is exposed to ahydrofluoric acid based etching solution (e.g. a 6:1 buffered oxide etchsolution). A specific test structure was used to demonstrate thebenefits of methods according to disclosed embodiments on in-trench filmquality. The structure has 60-120 nm width trenches and open areas.

FIGS. 2A-2B are cross-sectional schematics of an etched gapfill siliconoxide film and an etched gapfill silicon oxide film processed accordingto disclosed embodiments. The schematic in FIG. 2A shows a supportsubstrate 200 with multiple trenches between trench walls 202. The fullwafer was deposited with a flowable silicon-and-nitrogen-containing filmwhich was then cured and annealed at 200° C.-400° C. in steam and at800° C.-1100° C. in N₂. The wafer was then planarized using CMP to thetop of trenches on the patterned substrate. A nitride stop layer waspresent to help stop the polishing at the desired location. The locationof the post-planarization dielectric interface is shown with dotted line201. After a wet etch for 10 seconds in a 6:1 BOE the remaining siliconoxide in the narrow trenches 204-1 and the recessed open area 205-1 isshown using solid lines. The amount of material removed may be referredto as the wet recess and is proportional to the WER. The wet recess maybe different in different regions, e.g. the recess may vary with thewidth of the trench. The etch rate of the narrow gapfill portions 204-1is greater than that of the wide gapfill portion 205-1 resulting in thelower post-etch dielectric interface. The wet recess was about 90 nm innarrow trenches having 65 nm trench width and about 36 nm in the openarea.

Another wet etch rate comparison after a post-CMP anneal (in an inertenvironment) is shown in FIG. 2B. The heights of the narrow gapfillportions 204-2 and wide gapfill portion 205-2 are now similar because ofthe increased density in the narrow gapfill portion. The wet recess inthe different regions are substantially matched in the cross-sectionalschematic of FIG. 2B. The wet recess was reduced to 34 nm in the narrowtrenches and to 30 nm in the open area.

The density of both the narrow gapfill portions 204-2 and the widegapfill portion 205-2 have increased during the post-CMP anneal,however, the density in the narrow gapfill portion increased moresignificantly. This allows the WER of the narrow gapfill portion tobecome more similar to the WER of the wide gapfill portion. The etchrate of the wide gapfill portion, after treating the substrate toincrease a density, is within one of 20%, 15%, 10%, 7%, 5% or 3% of theetch rate of the narrow gapfill portion.

The methods presented herein are described using an exemplarysilicon-and-nitrogen-containing film which is subsequently treated tobecome a silicon oxide film. It should be noted that the methods may beused on silicon oxide as well as other dielectric gapfill films (e.g.SiON, SiOC) deposited using a variety of methods including SACVD,HARP/eHARP films (also known as TEOS-ozone silicon oxide/TEOS-ozone-H₂Osilicon oxide), Spin-On-Glass (SOG), Plasma-Enhanced CVD (PECVD) siliconoxide, Flowable CVD (FCVD) silicon oxide, Sub-Atmospheric CVD (SACVD)silicon oxide. The films may be undoped silicate glass (USG) or may bedoped (e.g. Boron-Phosphate Silicate Glass—BPSG). Increasing the densitywithin a trench and recessed open areas may involve re-flowing thegapfill material or healing the seam which may form during conformaldeposition.

Thermal treatments, such as curing and annealing, are not the only wayto increase the density of gapfill silicon oxide within trenches andrecessed open areas. Exciting a plasma in a substrate processing regioncontaining the patterned substrate can be used as a replacement for orin addition to the thermal steps (curing and/or annealing) describedpreviously. Such a plasma has also been found to increase the density ofgapfill silicon oxide. Plasma and thermal treatments can be performedconcurrently and/or sequentially. The plasma treatment can be performedin a separate plasma chamber or in the same chamber used for the otherprocesses described herein. FIG. 3 is a flowchart showing selected stepsin methods 300 of processing silicon oxide films according toembodiments of the invention. The method 300 includes planarizing agapfill silicon oxide layer 302 as in operation 110 of FIG. 1. Thepatterned substrate is then treated in an oxygen-containing plasma 304formed from oxygen-containing precursors; exemplary oxygen-containingprecursors were listed in the discussion pertaining to operation 108(and 112) of FIG. 1. The oxygen-containing precursors will typically beaccompanied by inert gases such as noble gases (Ne, Ar, etc.).Plasma-excited inert gases substantially without any oxygen-containingprecursors have also been found to increase the density of gapfillsilicon oxide following a planarization step. Plasma-excited inert gaseshaving both oxygen-containing precursors and hydrogen-containingprecursors have also been found to be helpful possibly as a result ofthe increase in moisture. All these plasma-based processes have beenfound to increase the density and produce more similar densities withinnarrow trenches and recessed open areas. The exemplary process of FIG. 3continues when the silicon oxide gapfill layer is annealed 306 tofurther densify and homogenize the gapfill layer. When the plasmaprocess and the thermal processes are sequentially applied, the plasmaprocess may precede or follow the thermal process.

During the plasma densification process, a plasma is created in thesubstrate processing region containing the substrate. Inert and reactiveprecursors (optionally) are flowed into the substrate processing regionand plasma power (e.g. RF or microwave) is applied to the region toexcite the gases. Plasma power may be applied in a variety of waysincluding capacitively and inductively. In some embodiments, RF powermay be supplied as a mixed frequency that typically supplies power at ahigh RF frequency (RF1) of 13.56 MHz and a low RF frequency (RF2) of 360KHz to enhance the decomposition of reactive species introduced intosubstrate processing region. The specific frequencies used may vary bylocale and are largely determined by communication interferenceconsiderations.

The temperature of the substrate may be greater than about 100° C.,about 150° C., about 200° C., about 250° C. or about 300° C., indisclosed embodiments. The temperature of the substrate may be less thanabout 600° C., about 500° C. or about 400° C., in disclosed embodiments.Any of the upper limits on substrate temperature may be combined withany of the lower limits to form additional temperature ranges accordingto additional disclosed embodiments. The pressure in the substrateprocessing region may be greater than about 0.5 Torr, 1 Torr, 2 Torr, or4 Torr, in disclosed embodiments. The pressure in the substrateprocessing region may be below about 20 Torr, about 15 Torr, about 10Torr, about 8 Torr or about 6 Torr, in disclosed embodiments. Additionaldisclosed embodiments may be formed by combining any of the lower limitson pressure with any of the upper limits. When ˜13.56 MHz is used toexcite the plasma, the RF power may be between about 25 Watts and about400 Watts, between about 50 Watts and about 350 Watts, between about 100Watts and about 300 Watts or between about 150 Watts and about 250 Wattsin disclosed embodiments. Any of the upper limits on RF power can becombined with any of the lower limits to form additional ranges forpower in additional disclosed embodiments.

Exemplary Substrate Processing System

Embodiments of the deposition systems may be incorporated into largerfabrication systems for producing integrated circuit chips. FIG. 4 showsone such system 400 of deposition, baking and curing chambers accordingto disclosed embodiments. In the figure, a pair of FOUPs (front openingunified pods) 402 supply substrate substrates (e.g., 300 mm diameterwafers) that are received by robotic arms 404 and placed into a lowpressure holding area 406 before being placed into one of the waferprocessing chambers 408 a-f. A second robotic arm 410 may be used totransport the substrate wafers from the holding area 406 to theprocessing chambers 408 a-f and back.

The processing chambers 408 a-f may include one or more systemcomponents for depositing, annealing, curing and/or etching a flowabledielectric film on the substrate wafer. In one configuration, two pairsof the processing chamber (e.g., 408 c-d and 408 e-f) may be used todeposit the flowable dielectric material on the substrate, and the thirdpair of processing chambers (e.g., 408 a-b) may be used to anneal thedeposited dielectric. In another configuration, the same two pairs ofprocessing chambers (e.g., 408 c-d and 408 e-f) may be configured toboth deposit and anneal a flowable dielectric film on the substrate,while the third pair of chambers (e.g., 408 a-b) may be used for UV orE-beam curing of the deposited film. In still another configuration, allthree pairs of chambers (e.g., 408 a-f) may be configured to deposit ancure a flowable dielectric film on the substrate. In yet anotherconfiguration, two pairs of processing chambers (e.g., 408 c-d and 408e-f) may be used for both deposition and UV or E-beam curing of theflowable dielectric, while a third pair of processing chambers (e.g. 408a-b) may be used for annealing the dielectric film. It will beappreciated, that additional configurations of deposition, annealing andcuring chambers for flowable dielectric films are contemplated by system400.

In addition, one or more of the process chambers 408 a-f may beconfigured as a wet treatment chamber. These process chambers includeheating the flowable dielectric film in an atmosphere that includesmoisture. Thus, embodiments of system 400 may include wet treatmentchambers 408 a-b and anneal processing chambers 408 c-d to perform bothwet and dry anneals on the deposited dielectric film.

FIG. 5A is a substrate processing chamber 500 according to disclosedembodiments. A remote plasma system (RPS) 510 may process a gas whichthen travels through a gas inlet assembly 511. Two distinct gas supplychannels are visible within the gas inlet assembly 511. A first channel512 carries a gas that passes through the remote plasma system RPS 510,while a second channel 513 bypasses the RPS 500. The first channel 502may be used for the process gas and the second channel 513 may be usedfor a treatment gas in disclosed embodiments. The lid (or conductive topportion) 521 and a perforated partition 553 are shown with an insulatingring 524 in between, which allows an AC potential to be applied to thelid 521 relative to perforated partition 553. The process gas travelsthrough first channel 512 into chamber plasma region 520 and may beexcited by a plasma in chamber plasma region 520 alone or in combinationwith RPS 510. The combination of chamber plasma region 520 and/or RPS510 may be referred to as a remote plasma system herein. The perforatedpartition (also referred to as a showerhead) 553 separates chamberplasma region 520 from a substrate processing region 570 beneathshowerhead 553. Showerhead 553 allows a plasma present in chamber plasmaregion 520 to avoid directly exciting gases in substrate processingregion 570, while still allowing excited species to travel from chamberplasma region 520 into substrate processing region 570.

Showerhead 553 is positioned between chamber plasma region 520 andsubstrate processing region 570 and allows plasma effluents (excitedderivatives of precursors or other gases) created within chamber plasmaregion 520 to pass through a plurality of through holes 556 thattraverse the thickness of the plate. The showerhead 553 also has one ormore hollow volumes 551 which can be filled with a precursor in the formof a vapor or gas (such as a silicon-containing precursor) and passthrough small holes 555 into substrate processing region 570 but notdirectly into chamber plasma region 520. Showerhead 553 is thicker thanthe length of the smallest diameter 550 of the through-holes 556 in thisdisclosed embodiment. In order to maintain a significant concentrationof excited species penetrating from chamber plasma region 520 tosubstrate processing region 570, the length 526 of the smallest diameter550 of the through-holes may be restricted by forming larger diameterportions of through-holes 556 part way through the showerhead 553. Thelength of the smallest diameter 550 of the through-holes 556 may be thesame order of magnitude as the smallest diameter of the through-holes556 or less in disclosed embodiments.

In the embodiment shown, showerhead 553 may distribute (via throughholes 556) process gases which contain oxygen, hydrogen and/or nitrogenand/or plasma effluents of such process gases upon excitation by aplasma in chamber plasma region 520. In embodiments, the process gasintroduced into the RPS 510 and/or chamber plasma region 520 throughfirst channel 512 may contain one or more of oxygen (O₂), ozone (O₃),N₂O, NO, NO₂, NH₃, N_(x)H_(y) including N2H4, silane, disilane, TSA andDSA. The process gas may also include a carrier gas such as helium,argon, nitrogen (N₂), etc. The second channel 513 may also deliver aprocess gas and/or a carrier gas, and/or a film-curing gas used toremove an unwanted component from the growing or as-deposited film.Plasma effluents may include ionized or neutral derivatives of theprocess gas and may also be referred to herein as a radical-oxygenprecursor and/or a radical-nitrogen precursor referring to the atomicconstituents of the process gas introduced.

In embodiments, the number of through-holes 556 may be between about 60and about 2000. Through-holes 556 may have a variety of shapes but aremost easily made round. The smallest diameter 550 of through holes 556may be between about 0.5 mm and about 20 mm or between about 1 mm andabout 6 mm in disclosed embodiments. There is also latitude in choosingthe cross-sectional shape of through-holes, which may be made conical,cylindrical or a combination of the two shapes. The number of smallholes 555 used to introduce a gas into substrate processing region 570may be between about 100 and about 5000 or between about 500 and about2000 in different embodiments. The diameter of the small holes 555 maybe between about 0.1 mm and about 2 mm.

FIG. 5B is a bottom view of a showerhead 553 for use with a processingchamber according to disclosed embodiments. Showerhead 553 correspondswith the showerhead shown in FIG. 5A. Through-holes 556 are depictedwith a larger inner-diameter (ID) on the bottom of showerhead 553 and asmaller ID at the top. Small holes 555 are distributed substantiallyevenly over the surface of the showerhead, even amongst thethrough-holes 556 which helps to provide more even mixing than otherembodiments described herein.

An exemplary film is created on a substrate supported by a pedestal (notshown) within substrate processing region 570 when plasma effluentsarriving through through-holes 556 in showerhead 553 combine with asilicon-containing precursor arriving through the small holes 555originating from hollow volumes 551. Though substrate processing region570 may be equipped to support a plasma for other processes such ascuring, no plasma is present during the growth of the exemplary film.

A plasma may be ignited either in chamber plasma region 520 aboveshowerhead 553 or substrate processing region 570 below showerhead 553.An AC voltage typically in the radio frequency (RF) range is appliedbetween the conductive top portion 521 of the processing chamber andshowerhead 553 to ignite a plasma in chamber plasma region 520 duringdeposition. The top plasma is left at low or no power when the bottomplasma in the substrate processing region 570 is turned on to eithercure a film or clean the interior surfaces bordering substrateprocessing region 570. A plasma in substrate processing region 570 isignited by applying an AC voltage between showerhead 553 and thepedestal or bottom of the chamber. A cleaning gas may be introduced intosubstrate processing region 570 while the plasma is present.

The radical nitrogen precursor is created in the remote plasma regionand travels into the substrate processing region where thesilicon-containing precursor is excited by the radical nitrogenprecursor. In embodiments, the silicon-containing precursor is excitedonly by the radical nitrogen precursor. Plasma power may essentially beapplied only to the remote plasma region, in embodiments, to ensure thatthe radical nitrogen precursor provides the predominant excitation tothe silicon-containing precursor.

In embodiments employing a chamber plasma region, the excited plasmaeffluents are generated in a section of the substrate processing regionpartitioned from a deposition region where the precursors mix and reactto deposit the silicon-and-nitrogen layer on a deposition substrate(e.g., a semiconductor wafer). The excited plasma effluents are alsoaccompanied by a unexcited inert gases (in the exemplary case, argon).The substrate processing region may be described herein as “plasma-free”during the growth of the silicon-and-nitrogen-containing layer, forexample. “Plasma-free” does not necessarily mean the region is devoid ofplasma. Ionized species and free electrons created within the plasmaregion do travel through pores (apertures) in the partition (showerhead)but the carbon-free silicon-containing precursor is not substantiallyexcited by the plasma power applied to the plasma region. The borders ofthe plasma in the chamber plasma region are hard to define and mayencroach upon the substrate processing region through the apertures inthe showerhead. In the case of an inductively-coupled plasma, a smallamount of ionization may be effected within the substrate processingregion directly. Furthermore, a low intensity plasma may be created inthe substrate processing region without eliminating desirable featuresof the forming film. All causes for a plasma having much lower intensityion density than the chamber plasma region (or a remote plasma region,for that matter) during the creation of the excited plasma effluents donot deviate from the scope of “plasma-free” as used herein.

The substrate may be heated in an inert atmosphere in a thermaldensification process. The heat may be supplied by the pedestal whichmay contain a resistive heating element to raise the substratetemperature. During a plasma densification process, an RF power supply540 applies electrical power between showerhead 553 and the pedestalbeneath the components pictured in FIG. 5A. The plasma power excites theprocess gas mixture to form a plasma within the roughly cylindricalregion between showerhead 553 and the substrate supported by pedestal.Showerhead 553 has either a conducting surface or the surface may beinsulating and covering a metal insert. Regardless of position, themetal portion of showerhead 553 is electrically isolated from the restof CVD chamber 500 via dielectric inserts which allow the voltage ofshowerhead 553 to be varied with respect to the support pedestal and lid520. The lid 521 and support pedestal are also electrically separated soa plasma can be created in substrate processing region 570 withoutcreating a plasma in chamber plasma region 520.

The substrate processing system is controlled by a system controller. Inan exemplary embodiment, the system controller includes a hard diskdrive, a floppy disk drive and a processor. The processor contains asingle-board computer (SBC), analog and digital input/output boards,interface boards and stepper motor controller boards. Various parts ofCVD system conform to the Versa Modular European (VME) standard whichdefines board, card cage, and connector dimensions and types. The VMEstandard also defines the bus structure as having a 16-bit data bus anda 24-bit address bus.

The system controller controls all of the activities of the CVD machine.The system controller executes system control software, which is acomputer program stored in a computer-readable medium. Preferably, themedium is a hard disk drive, but the medium may also be other kinds ofmemory. The computer program includes sets of instructions that dictatethe timing, mixture of gases, chamber pressure, chamber temperature, RFpower levels, susceptor position, and other parameters of a particularprocess. Other computer programs stored on other memory devicesincluding, for example, a floppy disk or other another appropriatedrive, may also be used to instruct the system controller.

A process for depositing a film stack on a substrate or a process forcleaning a chamber can be implemented using a computer program productthat is executed by the system controller. The computer program code canbe written in any conventional computer readable programming language:for example, 68000 assembly language, C, C++, Pascal, Fortran or others.Suitable program code is entered into a single file, or multiple files,using a conventional text editor, and stored or embodied in a computerusable medium, such as a memory system of the computer. If the enteredcode text is in a high level language, the code is compiled, and theresultant compiler code is then linked with an object code ofprecompiled Microsoft Windows® library routines. To execute the linked,compiled object code the system user invokes the object code, causingthe computer system to load the code in memory. The CPU then reads andexecutes the code to perform the tasks identified in the program.

The interface between a user and the controller is via a flat-paneltouch-sensitive monitor. In the preferred embodiment two monitors areused, one mounted in the clean room wall for the operators and the otherbehind the wall for the service technicians. The two monitors maysimultaneously display the same information, in which case only oneaccepts input at a time. To select a particular screen or function, theoperator touches a designated area of the touch-sensitive monitor. Thetouched area changes its highlighted color, or a new menu or screen isdisplayed, confirming communication between the operator and thetouch-sensitive monitor. Other devices, such as a keyboard, mouse, orother pointing or communication device, may be used instead of or inaddition to the touch-sensitive monitor to allow the user to communicatewith the system controller.

As used herein “substrate” may be a support substrate with or withoutlayers formed thereon. The support substrate may be an insulator or asemiconductor of a variety of doping concentrations and profiles andmay, for example, be a semiconductor substrate of the type used in themanufacture of integrated circuits. “Silicon oxide” and“silicon-and-oxygen-containing layer” are used interchangeably hereinand may include significant concentrations of other elementalconstituents such as nitrogen, hydrogen, carbon and the like. A gas inan “excited state” as used herein describes a gas wherein at least someof the gas molecules are in vibrationally-excited, dissociated and/orionized states. A gas may be a combination of two or more gases. Theterm trench is used throughout with no implication that the etchedgeometry necessarily has a large horizontal aspect ratio. Viewed fromabove the surface, trenches may appear circular, oval, polygonal,rectangular, or a variety of other shapes. The term “precursor” is usedto refer to any process gas which takes part in a reaction to eitherremove or deposit material from a surface. The phrase “inert gas” refersto any gas which does not form chemical bonds when incorporated into afilm. Exemplary inert gases include noble gases but may include othergases so long as no chemical bonds are formed when (typically) traceamounts are trapped in a film. As used herein, a conformal layer refersto a generally uniform layer of material on a surface in the same shapeas the surface, i.e., the surface of the layer and the surface beingcovered are generally parallel. A person having ordinary skill in theart will recognize that the deposited material likely cannot be 100%conformal and thus the term “generally” allows for acceptabletolerances.

Densities have been evaluated herein by measuring the wet etch rate(WER) and calculating a wet etch rate ratio (WERR). These measurementswere made by performing a timed etch in a hydrofluoric acid basedsolution and calculating the etch rate in nanometers per second. A WERRis typically created by comparing the etch rate of a dielectric samplewith that of a thermal silicon oxide in the same solution. A commonbuffered oxide etch solution includes a 6:1 volume ratio of 40% NH₄F inwater to 49% HF in water. This solution will etch thermally grownsilicon oxide at approximately 2 nanometres per second at 25° C. Othermethods of forming silicon oxide will typically result in silicon oxidefilms having faster wet etch rates. Faster wet etch rates generallyimply that the candidate silicon oxide film has a lower density thanthermally grown silicon oxide. In some cases, a wet etch rate ratio willbe used to compare two non-thermal silicon oxide films (or differentportions of the same film) and the context will make the distinction.

Having described several embodiments, it will be recognized by those ofskill in the art that various modifications, alternative constructions,and equivalents may be used without departing from the spirit of theinvention. Additionally, a number of well-known processes and elementshave not been described in order to avoid unnecessarily obscuring thepresent invention. Accordingly, the above description should not betaken as limiting the scope of the invention.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimits of that range is also specifically disclosed. Each smaller rangebetween any stated value or intervening value in a stated range and anyother stated or intervening value in that stated range is encompassed.The upper and lower limits of these smaller ranges may independently beincluded or excluded in the range, and each range where either, neitheror both limits are included in the smaller ranges is also encompassedwithin the invention, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded.

As used herein and in the appended claims, the singular forms “a”, “an”,and “the” include plural referents unless the context clearly dictatesotherwise. Thus, for example, reference to “a process” includes aplurality of such processes and reference to “the precursor” includesreference to one or more precursor and equivalents thereof known tothose skilled in the art, and so forth.

Also, the words “comprise,” “comprising,” “include,” “including,” and“includes” when used in this specification and in the following claimsare intended to specify the presence of stated features, integers,components, or steps, but they do not preclude the presence or additionof one or more other features, integers, components, steps, acts, orgroups.

1. A method of processing a silicon-and-oxygen-containing layer on apatterned substrate having a narrow trench and a recessed open area, themethod comprising: forming a carbon-free silicon-and-nitrogen-containinglayer on the patterned substrate including in the narrow trench and inthe recessed open area by chemical vapor deposition and converting thecarbon-free silicon-and-nitrogen-containing layer to thesilicon-and-oxygen-containing layer; planarizing thesilicon-and-oxygen-containing layer leaving a narrow gapfill portion inthe narrow trench and a wide gapfill portion in the recessed open area,wherein planarizing the silicon-and-oxygen-containing layer comprisesremoving a portion of the silicon-and-oxygen-containing layer above thenarrow trench and exposing a post-planarization dielectric interfacedisposed closer to the narrow trench than a correspondingpre-planarization dielectric interface; and treating the substrate,after the planarizing operation, to increase a density of the narrowgapfill portion, wherein the post-planarization dielectric interfacedisposed closer to the narrow trench allows the narrow gapfill portionto become denser than had the substrate been treated before theplanarizing operation.
 2. The method of claim 1 wherein forming thesilicon-and-oxygen-containing layer comprises: flowing a plasmaprecursor into a remote plasma region to form plasma effluents;combining the plasma effluents with a flow of a silicon-containingprecursor in a substrate processing region, wherein the flow of thesilicon-containing precursor has not been excited by a plasma; andcuring the silicon-and-nitrogen-containing layer in an ozone containingatmosphere to convert the layer into a silicon-and-oxygen-containinglayer.
 3. The method of claim 1 wherein the open area is a wide trenchhaving a width greater than one of 50 nm, 100 nm, 200 nm, 500 nm or 1000nm.
 4. The method of claim 1 wherein the narrow trench has a width lessthan one of 100 nm, 70 nm, 50 nm, 35 nm, 25 nm or 20 nm.
 5. The methodof claim 1 wherein the etch rate of the wide gapfill portion, aftertreating the substrate to increase a density, is within one of 20%, 15%,10%, 7%, 5% or 3% of the etch rate of the narrow gapfill portion.
 6. Themethod of claim 1 wherein the operation of treating the substrate toincrease a density comprises exposing the substrate to a plasma in anatmosphere comprising an inert gas.
 7. The method of claim 6 wherein theatmosphere further comprises oxygen.
 8. The method of claim 7 whereinthe atmosphere further comprises hydrogen.
 9. The method of claim 1wherein the operation of treating the substrate to increase a densitycomprises annealing the substrate above or about 400° C., 500° C., 600°C., 700° C. or 800° C. increase the density of the narrow gapfillportion.
 10. The method of claim 1 wherein the operation of planarizingthe silicon-and-oxygen-containing layer comprises chemical-mechanicallypolishing the substrate.
 11. The method of claim 1 wherein the operationof planarizing the silicon-and-oxygen-containing layer comprisesperforming a planarizing etch on the substrate.
 12. The method of claim1 wherein the operation of treating the substrate to increase a densityalso results in an increase in density of the wide gapfill portion. 13.The method of claim 1 wherein the operation of treating the substrate toincrease a density comprises sequentially exposing the substrate to aplasma and then annealing the substrate.
 14. The method of claim 1wherein the operation of treating the substrate to increase a densitycomprises sequentially annealing the substrate and then exposing thesubstrate to a plasma.
 15. The method of claim 1 further comprisingannealing the silicon-and-oxygen-containing layer in anoxygen-containing atmosphere at a substrate temperature greater than oneof 500° C., 600° C., 700° C. or 800° C. before planarizing thesilicon-and-oxygen-containing layer.
 16. The method of claim 1 whereinthe silicon-and-oxygen-containing layer consists essentially of siliconand oxygen after the operation of treating thesilicon-and-oxygen-containing layer.